240
S. Okajima et al. / Journal of Organometallic Chemistry 656 (2002) 234ꢀ242
/
4.5. General procedure for the preparation of
diastereomerically pure Sb(R)- and Sb(S)-(aryl)[2-
(S)-(1-dimethylaminoethyl)phenyl](p-tolyl)stibanes
(4b, c) from the palladium complexes (6b, c)
4.5.3. Sb(R or S)-[2-(S)-(1-dimethylaminoethyl)-
phenyl](9-phenanthryl)(p-tolyl)stibanes (4c-A)
Colorless prisms (ethanolꢀ
155 8C, 99% yield. 1H-NMR (500 MHz) d: 1.37 (3H, d,
Jꢂ6.9 Hz), 1.77 (6H, s), 2.33 (3H, s), 3.90 (1H, q, Jꢂ
6.9 Hz), 7.03 (1H, t, Jꢂ6.9 Hz), 7.10 (2H, d, Jꢂ7.8
Hz), 7.26 (1H, t, Jꢂ6.4 Hz), 7.27 (1H, t, Jꢂ7.4 Hz),
7.34 (1H, d, Jꢂ7.3 Hz), 7.39 (2H, d, Jꢂ7.8 Hz), 7.47
(1H, t, Jꢂ6.9 Hz), 7.49 (1H, t, Jꢂ7.8 Hz), 7.58 (1H, t,
Jꢂ7.3 Hz), 7.59 (2H, d, Jꢂ7.8 Hz), 7.63 (1H, s), 8.23
(1H, d, Jꢂ6.9 Hz), 8.66 (1H, d, Jꢂ8.2 Hz), 8.71 (1H,
d, Jꢂ
7.8 Hz). 13C-NMR (125 MHz) d: 11.10 (q), 21.41
/
benzene 10:1), m.p. 153ꢀ
/
/
/
To a stirred solution of the diastereomerically pure
palladium complexes (6b-A, 6b-B, 6c-A, and 6c-B; 1
mmol) in dichloromethane (30 ml) were added solids of
triphenylphosphine (288 mg, 1.1 mmol) in small por-
tions at r.t. and the mixture was stirred for 10 min. The
reaction mixture was concentrated in vacuo and the
resulting residue was subjected to column chromato-
graphy on silica gel using a mixture of ether and
dichloromethane (1:10) as an eluent to give the corre-
sponding diastereomerically pure (aryl)[2-(S)-(1-di-
methylaminoethyl)phenyl](p-tolyl)stibanes 4b-A, 4b-B,
4c-A, and 4c-B, respectively.
/
/
/
/
/
/
/
/
/
/
/
/
/
(q), 39.71 (q), 63.25 (d), 122.42 (d), 122.95 (d), 126.01
(d), 126.08 (d), 126.27 (d), 126.36 (d), 127.35 (d), 128.14
(d), 128.45 (d), 129.24 (d), 130.02 (s), 130.17 (d), 130.46
(s), 132.07 (d), 136.45 (s, 2C), 136.97 (d), 137.44 (s),
137.48 (s), 137.758 (s), 137.761 (d), 139.60 (s), 141.88 (s),
149.00 (s). [a]2D5: ꢁ
38.38 (c 2, benzene). EIMS (relative
/
intensity) m/z: 537 [Mꢁ, 4], 446 (37), 360 (base), 267 (8),
178 (16), 91 (7). EIHRMS m/z: 537.1414 (Calc. for
C31H30NSb: 537.1416). Anal. Calc. for C31H30NSb: C,
69.16; H, 5.62; N, 2.60. Found: C, 69.14; H, 5.69; N,
2.73%.
4.5.1. Sb(R)-[2-(S)-(1-dimethylaminoethyl)-
phenyl](1-naphthyl)(p-tolyl)stibane (4b-A)
Colorless oil, 98% yield. 1H-NMR (500 MHz) d: 1.37
(3H, d, Jꢂ
q, Jꢂ6.9 Hz), 7.04 (1H, t, Jꢂ
7.3 Hz), 7.24ꢀ7.43 (9H, m), 7.77 (1H, d, Jꢂ
7.82 (1H, d, Jꢂ7.8 Hz), 8.19 (1H, d, Jꢂ
8.2 Hz). 13C-
/
6.9 Hz), 1.74 (6H, s), 2.31 (3H, s), 3.84 (1H,
6.9 Hz), 7.08 (2H, d, Jꢂ
8.2 Hz),
/
/
/
4.5.4. Sb(R or S)-[2-(S)-(1-dimethylaminoethyl)-
phenyl](9-phenanthryl)(p-tolyl)stibanes (4c-B)
Colorless oil, 99% yield. 1H-NMR (500 MHz) d: 1.41
/
/
/
/
NMR (125 MHz) d: 11.58 (q), 21.36 (q), 39.84 (q), 63.49
(d), 125.35 (d), 125.49 (d), 125.98 (d), 126.14 (d), 127.30
(d), 128.10 (d), 128.17 (d), 128.68 (d), 129.18 (d), 129.47
(d), 133.63 (s), 135.43 (d), 136.42 (d), 137.37 (s), 137.752
(s), 137.756 (s), 138.11 (s), 139.57 (s), 143.00 (s), 149.14
(3H, d, Jꢂ
q, Jꢂ7.8 Hz), 7.07 (2H, d, Jꢂ
7.3 Hz), 7.26 (1H, t, Jꢂ7.8 Hz), 7.29 (1H, t, Jꢂ
7.33 (2H, d, Jꢂ7.8 Hz), 7.36 (1H, d, Jꢂ8.2 Hz), 7.48
(1H, t, Jꢂ7.8 Hz), 7.53 (1H, t, Jꢂ7.8 Hz), 7.56 (1H, d,
Jꢂ7.3 Hz), 7.59 (1H, d, Jꢂ8.8 Hz), 7.61 (1H, s), 7.62
(1H, t, Jꢂ8.8 Hz), 8.38 (1H, d, Jꢂ8.2 Hz), 8.67 (1H, d,
Jꢂ8.2 Hz), 8.73 (1H, d, Jꢂ
7.8 Hz). 13C-NMR (125
/
6.9 Hz), 1.77 (6H, s), 2.32 (3H, s), 3.80 (1H,
7.8 Hz), 7.09 (1H, t, Jꢂ
7.3 Hz),
/
/
/
/
/
/
/
/
/
(s). [a]2D4: ꢃ
63.38 (c 2, benzene). EIMS (relative inten-
/
/
/
sity) m/z: 487 [Mꢁ, 4], 396 (41), 360 (base), 217 (8), 148
(5), 128 (5), 91 (7). EIHRMS m/z: 487.1258 (Calc. for
C27H28NSb: 487.1260).
/
/
/
/
MHz) d: 12.55 (q), 21.33 (q), 40.32 (q), 63.92 (d), 122.39
(d), 122.96 (d), 126.04 (d), 126.26 (d), 126.36 (d), 127.41
(d), 128.20 (d), 128.40 (d), 129.28 (d), 130.01 (s), 130.27
(d), 130.35 (s), 132.01 (s), 136.33 (s,), 136.56 (d, 2C),
136.78 (d), 137.44 (s), 137.60 (s), 138.02 (d), 139.60 (s),
4.5.2. Sb(S)-[2-(S)-(1-dimethylaminoethyl)phenyl](1-
naphthyl)(p-tolyl)stibane (4b-B)
Colorless prisms (hexane) m.p. 137ꢀ
/
138.5 8C, 98%
yield. H-NMR (500 MHz) d: 1.38 (3H, d, Jꢂ6.9 Hz),
1.73 (6H, s), 2.31 (3H, s), 3.80 (1H, q, Jꢂ6.9 Hz), 7.06
(1H, t, Jꢂ7.3 Hz), 7.09 (2H, d, Jꢂ7.3 Hz), 7.23ꢀ7.47
(9H, m), 7.77 (1H, d, Jꢂ8.2 Hz), 7.84 (1H, d, Jꢂ7.3
Hz), 8.34 (1H, d, Jꢂ
7.8 Hz). 13C-NMR d: 12.02 (q),
141.47 (s), 149.58 (s). [a]2D6: ꢁ
17.9 8 (c 2, benzene).
/
1
/
EIMS (relative intensity) m/z: 537 [Mꢁ, 3], 446 (30), 360
(base), 267 (8), 178 (12), 91 (6). EIHRMS m/z: 537.1415
(Calc. for C31H30NSb: 537.1416).
/
/
/
/
/
/
/
4.6. Crystallography
21.35 (q), 40.10 (q), 63.65 (d), 125.38 (d), 125.60 (d),
126.00 (d), 126.17 (d), 127.35 (d), 128.07 (d), 128.11 (d),
128.68 (d), 129.25 (d), 129.65 (d), 133.62 (s), 135.21 (d),
136.52 (d), 137.35 (s), 137.94 (s, 2C), 137.94 (s), 139.75
4.6.1. Data collection and refinement
Data were collected on a CCD area detector (Bruker
Smart 1000, Bruker AXS, Madison, WI, USA) with
(s), 142.71 (s), 149.48 (s). [a]2D5: ꢁ
/
53.8 8 (c 2, benzene).
graphite monochromated Moꢀ
0.71070 A). The structure was solved by direct methods
/
Ka radiation (lꢂ
/
EIMS (relative intensity) m/z: 487 [Mꢁ, 3], 396 (34), 360
(base), 217 (7), 148 (5), 128 (5), 91 (6). EIHRMS m/z:
487.1257 (Calc. for C27H28NSb: 487.1260). Anal. Calc.
for C27H28NSb: C, 66.41; H, 5.78; N, 2.87. Found: C,
66.61; H, 5.86; N, 3.02%.
˚
(
(
SIR-92) [16] and expanded using Fourier techniques
DIRDIF-94) [17]. The structure was refined by the full-
matrix least-squares procedures. The non-hydrogen
atoms were refined using anisotropic displacement